6533b831fe1ef96bd1299896
RESEARCH PRODUCT
Cationic and Anionic Impact on the Electronic Structure of Liquid Water
Ludger InhesterAnnette PietzschPhilippe WernetAlexander FöhlischAlexander FöhlischZhong YinSimone TechertSimone TechertWilson QuevedoGerrit GroenhofSreevidya Thekku VeeduHelmut Grubmüllersubject
hydration cellsAb initio02 engineering and technologyElectronic structure010402 general chemistry01 natural sciencesBathochromic shiftMoleculeGeneral Materials ScienceEmission spectrumPhysical and Theoretical ChemistrySpectroscopyta116Lone pairliquid waterta114ionitChemistryInstitut für Physik und Astronomie021001 nanoscience & nanotechnologyelectronic structure0104 chemical sciencesSolvation shell13. Climate actionChemical physicsionsAtomic physics0210 nano-technologydescription
Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water–ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl– ions causes an additional peak in the water emission spectrum at around 528 eV. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-01-01 |